Aminofunctional organosiloxanes

ABSTRACT

Aminofunctional silicone compositions are disclosed comprising: an organopolysiloxane having an average formula of (CH3)3SiO[(CH3)2SiO]x [(CH3)RNSiO]ySi(CH3)3 with less than 1 weight % of nitrogen in its formula, where RN is an aminofunctional group, x is ≥100, y is ≥1 with the proviso the sum of x+y is from 250 to 350; wherein the viscosity of the silicone composition ranges from 1000 to 2500 cP at 25° C. and is measured by a Brookfield RV DV viscometer equipped with Pro CP 52 spindle at 20 RPM; and the aminofunctional silicone composition contains less than 0.1 weight % of D4 and less than 0.1 weight % D5 cyclic siloxanes.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of National Stage application Ser.No. 14/349,674 as filed on Apr. 4, 2014, now U.S. Pat. No. 9,849,309 B2,which claims priority to and all advantages of International ApplicationNo. PCT/US2012/066958 as filed on Nov. 29, 2012, which claims priorityto and all advantages of U.S. Provisional Patent Application No.61/564,426 as filed on Nov. 29, 2011, the contents of which are herebyincorporated by reference.

BACKGROUND

Aminofunctional silicones are widely used in hair care products toprovide various aesthetic benefits. Formulators of hair care productsare continuously seeking improvements in consumer perceivable benefitsof such products. As such, there is an ongoing need to identify newaminofunctional silicones that can provide consumer perceivedconditioning benefits in a variety of hair care formulations. Anyimproved aminofunctional silicone composition should also be easilyincorporated into hair care products while not affecting the storagestability of the product. In particular, certain silicones may reducethe viscosity of hair care products upon storage. Thus, there is afurther need to identify aminofunctional silicone compositions thatprovide consumer perceivable conditioning benefits in formulated haircare products that are storage stabile.

Reducing the presence of solvents, un-reacted siloxanes, catalystresidues, cyclic polymerization byproducts, and other impurities inaminofunctional silicones is another ongoing challenge in the art. Theneed to reduce such impurities may arise, among other reasons, when suchimpurities are incompatible with downstream applications (for example,medical, cosmetic, and personal care applications), where the presenceof such impurities would reduce the stability of the product, or whereregulatory requirements require removal or reduction of their presence.In particular, there is an interest to reduce the presence ofcyclosiloxanes, such as octamethylcyclotetrasiloxanes (D4) anddecamethylcyclopentasiloxanes (D5), in aminofunctional siliconescompositions. In many instances D4 and D5 may be present in the processto prepare the aminofunctional silicones, alternatively they may beproduced from side reactions upon storing the aminofunctional siliconecomposition.

BRIEF SUMMARY

The present inventors have discovered certain aminofunctional siliconecompositions that provide consumer perceivable conditioning benefits informulated hair care products that are storage stable. Furthermore, thepresent aminofunctional silicone compositions have reduced D4 and D5cyclosiloxane contents.

The present aminofunctional silicone compositions comprise:

an organopolysiloxane having an average formula of(CH₃)₃SiO[(CH₃)₂SiO]_(x)[(CH₃)R^(N)SiO]_(y)Si(CH₃)₃with less than 1 weight % of nitrogen in its formula,where R^(N) is an aminofunctional group,x is ≥100, y is ≥1 with the proviso the sum of x+y is from 250 to 350;wherein the viscosity of the silicone composition ranges from 1000 to2500 cP at 25° C. as measured by a Brookfield RV DV viscometer equippedwith Pro CP 52 spindle at 20 RPM; and the aminofunctional siliconecomposition contains less than 0.1 weight % of D4 and less than 0.1weight % D5 cyclic siloxanes.

The present disclosure further provides emulsion compositions containingthe aminofunctional silicone compositions.

The present disclosure further relates to personal care productscontaining the aminofunctional silicone compositions or emulsionsthereof.

DETAILED DESCRIPTION

The present disclosure relates to aminofunctional silicone compositionscomprising, or alternatively consisting essentially of:

an organopolysiloxane having an average formula of(CH₃)₃SiO[(CH₃)₂SiO]_(x)[(CH₃)R^(N)SiO]_(y)Si(CH₃)₃with less than 1 weight % of nitrogen in its formula,where R^(N) is an aminofunctional group,x is ≥100, y is ≥1 with the proviso the sum of x+y is from 250 to 350;wherein the viscosity of the silicone composition ranges from 1000 to2500 cP at 25° C. and is preferentially measured by means of aBrookfield RV DV viscometer equipped with Pro CP 52 spindle at 20 RPM;and the aminofunctional silicone composition contains less than 0.1weight % of D4 and less than 0.1 weight % D5 cyclic siloxanes.

The organopolysiloxane in the present aminofunctional siliconecompositions have an average formula of (CH₃)₃SiO[(CH₃)₂SiO]_(x)[(CH₃)R^(N)SiO]_(y)Si(CH₃)₃. The x subscript in the above formuladenotes the number of (CH₃)₂SiO units present in the organopolysiloxane,and the y subscript denotes the number of (CH₃)R^(N)SiO units present inthe organopolysiloxane. The number of (CH₃)₂SiO units present in theorganopolysiloxane is equal to or greater than 100, that is x is ≥100,alternatively, x may vary from 100 to 340, alternatively from 200 to300. The number of (CH₃)R^(N)SiO units present in the organopolysiloxaneis equal to or greater than 1, that is y is ≥1, alternatively y may varyfrom 1 to 50, or alternatively from 1 to 20. The sum of x and yrepresents the “degree of polymerization” of the organopolysiloxane andshould be a value ranging from 250 to 350. The values of x and y may bedetermined using ²⁹Si NMR. Furthermore, the values of x and y may varyproviding the particular combination of (CH₃)₂SiO units and(CH₃)R^(N)SiO units in the organopolysiloxane provides theorganopolysiloxane with less than 1 weight % of nitrogen in its formula.As used herein, “weight % of nitrogen” refers to the amount of elementalN in the organopolysiloxane, as determined by analytical methods forassessing elemental nitrogen, such as titration and/or NMR.

The number average (M_(n)) and weight average (M_(w)) molecular weightof the organosiloxane may vary in accordance with the selection of theaminofunctional group and overall degree of polymerization. The numberaverage (M_(n)) may vary from 15,000 to 30,000 g/mole, alternativelyfrom 20,000 to 26,000, alternatively from 21,000 to 24,000. The weightaverage (M_(w)) may vary from 35,000 to 60,000 g/mole, alternativelyfrom 40,000 to 50,000 g/mole, alternatively from 40,000 to 45,000. Bothnumber and weight average molecular weight may be determined using gelpermeation chromatography (GPC) techniques using polystyrene standardsfor calibration.

The aminofunctional group is designated in the formulas herein as R^(N)and is illustrated by groups having the formula; —R⁵NHR⁶, —R⁵NR₂ ⁶, or—R⁵NHR⁵NHR⁶, wherein each R⁵ is independently a divalent hydrocarbongroup having at least 1 carbon atom, and R⁶ is hydrogen or an alkylgroup. Each R⁵ is typically an alkylene group having from 2 to 20 carbonatoms. R⁵ is illustrated by groups such as; —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂CHCH₃—, —CH₂CH₂CH₂CH₂—, —CH₂CH(CH₃)CH₂—, —CH₂CH₂CH₂CH₂CH₂—,—CH₂CH₂CH₂CH₂CH₂CH₂—, —CH₂CH₂CH(CH₂CH₃)CH₂CH₂CH₂—,—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—, and —CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—. In oneembodiment R⁶ is methyl.

Some examples of suitable amino-functional groups are; —CH₂CH₂NH₂,—CH₂CH₂CH₂NH₂, —CH₂CHCH₃NH, —CH₂CH₂CH₂CH₂NH₂, —CH₂CH₂CH₂CH₂CH₂NH₂,—CH₂CH₂CH₂CH₂CH₂CH₂NH₂, —CH₂CH₂NHCH₃, —CH₂CH₂CH₂NHCH₃,—CH₂(CH₃)CHCH₂NHCH₃, —CH₂CH₂CH₂CH₂NHCH₃, —CH₂CH₂NHCH₂CH₂NH₂,—CH₂CH₂CH₂NHCH₂CH₂NH₂, —CH₂CH₂CH₂NHCH₂CH₂CH₂NH₂,—CH₂CH₂CH₂CH₂NHCH₂CH₂CH₂CH₂NH₂, —CH₂CH₂NHCH₂CH₂NHCH₃,—CH₂CH₂CH₂NHCH₂CH₂CH₂NHCH₃, —CH₂CH₂CH₂CH₂NHCH₂CH₂CH₂CH₂NHCH₃, and—CH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂CH₃. In one embodiment, the amino functionalgroup is —CH₂CH₂CH₂NHCH₂CH₂NH₂.

The present aminofunctional silicone compositions contain less than 0.1weight % of D4 and D5 cyclic siloxanes. That is less than 0.1% wt for D4and independently less than 0.1% wt D5. Alternatively, % of D4 is lessthan 0.05% or alternatively less than 0.01%. D5 is less than 0.1% oralternatively less than 0.05% or alternatively less than 0.01%.

The weight % of the D4 and D5 cyclics in the silicone composition may bereadily determined by any analytical techniques, such as gaschromatography (GC) techniques.

The present disclosure further provides a process for preparing theaminofunctional silicone compositions by reacting:

a) a polydimethylsiloxane having the formula′HO(CH₃)₂SiO[(CH₃)₂SiO]_(x′)Si(CH₃)₂OH,where x′ is ≥10

b) a trimethysilyl endblocking compound, and

c) an aminofunctional alkoxysilane having the formula(R⁷O)₂(CH₃)SiR^(N).

The reaction in the above process is a condensation polymerizationreaction. The reaction may be effected by employing conditions known inthe art for effecting condensation reactions. Typically, such conditionsaffect hydrolysis of components b) and c), such that the hydrolyzedcomponents further condense with each other??? and component a). Thereaction effected in the present process may occur simultaneously, thatis, where all three component are mixed and reacted. Alternatively, thereaction may proceed in a stepwise manner as further described below.

Component a) in the above process is a polydimethylsiloxane having theformula:HO(CH₃)₂SiO[(CH₃)₂SiO]_(x′)Si(CH₃)₂OHwherein the subscript x′ represents the degree of polymerization (DP) ofthe polydimethylsiloxane. The value for x′ is equal to or greater than10, or may vary from 10 to 500, or alternatively from 10 to 200, oralternatively from 20 to 100, or alternatively from 30 to 60.Polydimethylsiloxanes of the above formula are known in the art and manyare commercially available.

Component b) in the above process is a trimethysilyl endblockingcompound. Component b) may be selected from those known in the art toact as endblocking groups for organopolysiloxanes. These include, butnot limited to; trimethylalkoxysilanes such as trimethylmethoxysilaneand trimethylethoxysilane; and hexamethyldisilazane.

Component c) in the above process is an aminofunctional alkoxysilanehaving the formula (R⁷O)₂(CH₃)SiR^(N), wherein R⁷ is an alkyl groupcontaining 1 to 4 carbons, and R^(N) is an aminofunctional group, asdefined above. Representative, non-limiting examples include;

(CH₃O)₂(CH₃)Si(CH₂)₃NH₂,

(CH₃O)₂(CH₃)Si(CH₂)₄NH₂,

(CH₃O)₂(CH₃)Si(CH₂)₃NH(CH₂)₂NH₂,

(CH₃O)₂(CH₃)SiCH₂CH(CH₃)CH₂NH(CH₂)₂NH₂,

(CH₃O)₂(CH₃)SiCH₂CH(CH₃)CH₂NH(CH₂)₃NH₂,

(CH₃O)₂(CH₃)Si(CH₂)₃NH(CH₂)₂NH(CH₂)₂NH₂,

(CH₃O)₂(CH₃)Si(CH₂)₃NH(CH₂)₄NH₂, and similar ethoxy (C₂H₅O) silanes. Theamino functional alkoxy silane c) may also be a mixture of two or moreindependent amino functional alkoxy silanes as described above.

In one embodiment of the present process, the amino functional alkoxysilane is (CH₃O)₂(CH₃)Si(CH₂)₃NH(CH₂)₂NH₂

The above reaction among components a), b), and c) may be carried out atany temperature in the range from 0 to 200° C. Temperatures of at least50° C. are preferred, most preferably from 60° C. up to 120° C. Thereaction may be carried out at pressures in the range from 5 mbar up to5 bar, for example at ambient pressure; it is frequently preferred thatat least the later part of the reaction is carried out under reducedpressure, for example 10 to 400 mbar, particularly if there is a need topromote removal of volatile byproducts from the reaction system.

The viscosity of the organopolysiloxane is preferentially measured at25° C.; by means of a Brookfield RV DV viscometer equipped with Pro CP52 spindle at 20 RPM. The same shear rate can be attained by commercialrheometers as, for example, but not restricted to Anton Paar MCR 301,AR1500 from TA instruments. For practical reasons the viscosity isfrequently expressed in cSt, that is the ratio between the absoluteviscosity measured by means of any of the above-mentioned instruments,expressed in Pa·s or alternatively in Poise) divided by the density ofthe material measured at the same temperature. It is known in the artthat the density of silicones at room temperature is in the range 0.96-1g/cm3. This means that the numerical values for the absolute andkinematic viscosity (expressed in cP and cSt respectively) are veryclose, although the units are not equivalent.

The present disclosure further relates to aqueous silicone emulsionscomprising:

A) the aminofunctional silicone composition, as described above,

B) a quaternary ammonium surfactant having a formulaR¹R²R³R⁴N⁺X⁻,

where R¹ is a radical containing at least 10 carbon atoms,

-   -   R² is R¹ or a hydrocarbyl containing 1 to 12 carbon atoms,        -   R³ is R¹, R², or an alcohol group containing 2 to 10 carbon            atoms,        -   R⁴ is R¹, R², or R³,        -   X⁻ is a halide, sulfate, sulfonate, methosulfate, or            ethosulfate, and            C) a nonionic surfactant.            In one embodiment, the aqueous silicone emulsion contains            less than 0.1 weight % of D4 and D5 cyclic siloxanes, and            upon ageing the emulsion for one month at 50° C. the content            of D4, D5 or both is lower than one of the following:

0.1 wt. % for D4 or 0.1 wt. % for D5 for the emulsion, below 0.14 for D4or 0.07 for D5, when the content is expressed as ratio of the

cyclic to the non-water content of the cationic surfactant, below 1.3for D4 when the content of the later is expressed as((D4_(AGED)−D4_((t=0)))/% CS)*100, where D4 is wt % the percentage of D4in the aged and starting emulsion respectively and % CS is the massfraction of the cationic surfactant (non-water content) in the emulsion.

The aminofunctional silicone composition used as component a) are thoseas described above, or may also be a combination of any of theaforementioned aminofunctional silicone compositions used in combinationwith other organopolysiloxanes. The aminofunctional organopolysiloxanemay also be dissolved in a suitable solvent, such as a lower molecularweight organopolysiloxane or organic solvent. The aminofunctionalorganopolysiloxane used as component a) may also be a blend or a mixtureof one or several of the aforementioned aminofunctionalorganopolysiloxanes with a OH-terminated or trimethyl- ortri-methyl/methoxy PDMS of viscosity of at least 350 cSt at 25° C.

Component B) in the present silicone emulsions is a quaternary ammoniumsurfactant having a formula R1 R2 R3 R4 N₊ X⁻,

where R¹ is a radical containing at least 10 carbon atoms,

-   -   R² is R¹ or a hydrocarbyl containing 1 to 12 carbon atoms,    -   R³ is R¹, R², or an alcohol group containing 2 to 10 carbon        atoms,    -   R⁴ is R¹, R², or R³,    -   X⁻ is a halide, sulfate, sulfonate, methosulfate, or        ethosulfate.

Alternatively the cationic surfactant may be a mixture of two or morequaternary ammonium species satisfying the description above.

The present emulsions further contain a nonionic surfactant as componentC). The nonionic surfactant may be selected from polyoxyethylene basedcompounds, such as those considered as ethoxylated alcohols.Representative examples of suitable commercially available nonionicsurfactants include polyoxyethylene fatty alcohols sold under thetradename BRIJ® by Croda (ICI Surfactants), Wilmington, Del. Someexamples are Brij® L23, an ethoxylated alcohol known as polyoxyethylene(23) lauryl ether, and Brij® L4, another ethoxylated alcohol known aspolyoxyethylene (4) lauryl ether. Some additional nonionic surfactantsinclude ethoxylated alcohols sold under the trademark TERGITOL® by TheDow Chemical Company, Midland, Mich. Some example are TERGITOL® TMN-6,an ethoxylated alcohol known as ethoxylated trimethylnonanol; andvarious of the ethoxylated alcohols, i.e., C₁₂-C₁₄ secondary alcoholethoxylates, sold under the trademarks TERGITOL® 15-S-5, TERGITOL®15-S-12, TERGITOL® 15-S-15, and TERGITOL® 15-S-40. Lutensol supplied byBASF in the series of Lutensol XP known as ethoxylated, C10-Guerbetalcohol and Lutensol TO known as ethoxylated, iso-C13 alcohol may alsobe used.

Surfactants whose hydrophilic moiety is based on saccaride orpolysaccaride can also be employed. Examples of these are Lutensol 8GD70 (BASF) and Triton BG-10 from The Dow Chemical Company (Midland,Mich.).

When mixtures containing nonionic surfactants are used, one nonionicsurfactant may have a low Hydrophile-Lipophile Balance (HLB) and theother nonionic surfactant may have a high HLB, such that the twononionic surfactants have a combined HLB of 11-15, alternatively acombined HLB of 12.5-14.5.

The amount of components A), B), C), and water in the emulsion may vary.Typically, the emulsions will contain;

15 to 80 wt. % of A) aminofunctional polyorganosiloxane,

alternatively 30 to 75% A) aminofunctional polyorganosiloxane,

or alternatively 47 to 71% A) aminofunctional polyorganosiloxane,

0.5 to 10 wt. % of B) quaternary ammonium surfactant,

alternatively 1.2 to 8 wt. % of B) quaternary ammonium surfactant,

or alternatively 1.3 to 6.7 wt. % of B) quaternary ammonium surfactant,2 to 8 wt. % of C) nonionic surfactant,

alternatively 3 to 7 wt. % of B) nonionic surfactant,

or alternatively 3.5 to 5.2 wt. % of B) nonionic surfactant,

and sufficient amounts of water, or other components, to sum to 100 wt%.

Other additives can also be incorporated in the emulsions of the presentdisclosure, such as fillers, viscosity modifiers, foam control agents;anti-freeze agents and biocides.

The present emulsions may be prepared by any known methods, oralternatively prepared by the methods as discussed below.

The present disclosure further provides a process for preparing anemulsion by;

-   -   I) forming a mixture comprising;        -   A) 100 parts by weight of an aminofunctional            organopolysiloxane,        -   B) 0.1 to 50 parts by weight of an a quaternary ammonium            surfactant,        -   C) 0.1 to 50 parts by weight of a non-ionic surfactant,            (components A, B, and C, are as described above)    -   II) admixing a sufficient amount of water to the mixture from        step I) to form an emulsion,    -   III) optionally, further shear mixing the emulsion and/or        diluting of the emulsion with the continuous phase.

The surfactants B) and C) may be added either alone or in combinationwith varying amounts of water in step I. Typically, when a surfactant orsurfactant combination is selected, the surfactant is added in step I asa concentrated aqueous dispersion, or alternatively as an aqueoussolution.

The amount of each surfactant added in step I should be 0.1 to 50 partsby weight for every 100 parts by weight of the aminofunctionalorganopolysiloxane used. Alternatively, the amount of each surfactantadded in step I may be 1 to 50 parts by weight for every 100 parts byweight of the aminofunctional organopolysiloxane used. Alternatively,the amount of surfactants added in step I may be 2 to 20 parts by weightfor every 100 parts by weight of the aminofunctional organopolysiloxaneused.

Mixing in step (I) can be accomplished by any method known in the art toeffect mixing of high viscosity materials. The mixing may occur eitheras a batch, semi-continuous, or continuous process. Mixing may occur,for example using, batch mixing equipments with medium/low shear includechange-can mixers, double-planetary mixers, conical-screw mixers, ribbonblenders, double-arm or sigma-blade mixers; batch equipments withhigh-shear and high-speed dispersers include those made by Charles Ross& Sons (NY), Hockmeyer Equipment Corp. (NJ); batch equipments with highshear actions include Banbury-type (CW Brabender Instruments Inc., NJ)and Henschel type (Henschel mixers America, TX); centrifugalforce-based, high shear mixing devices as for example Speed Mixer®(Hauschild & Co KG, Germany). Illustrative examples of continuousmixers/compounders include extruders single-screw, twin-screw, andmulti-screw extruders, co-rotating extruders, such as those manufacturedby Krupp Werner & Pfleiderer Corp (Ramsey, N.J.), and Leistritz (NJ);twin-screw counter-rotating extruders, two-stage extruders, twin-rotorcontinuous mixers, dynamic or static mixers or combinations of theseequipments.

The temperature and pressure at which the mixing of step I occurs is notcritical, but generally is conducted at ambient temperature andpressures. Typically, the temperature of the mixture will increaseduring the mixing process due to the mechanical energy associated whenshearing such high viscosity materials.

Step II of the process involves admixing water to the mixture of step Ito form an emulsion. Typically 5 to 2000 parts by weight water are mixedfor every 100 parts by weight of the step I mixture to form an emulsion.The water is added to the mixture from step I at such a rate, withadditional mixing, so as to form an emulsion of the mixture of step I.While this amount of water can vary depending on the selection of thesurfactants, generally the amount of water is from 0.1 to 2000 parts per100 parts by weight of the step I mixture, alternatively from 5 to 500parts per 100 parts by weight of the step I mixture, or alternativelyfrom 5 to 100 parts per 100 parts by weight of the step I mixture.

The water added to the mixture from step I may be done in incrementalportions, whereby each incremental portion comprises less than 30 weight% of the mixture from step I and each incremental portion of water isadded successively to the previous after the dispersion of the previousincremental portion of water, wherein sufficient incremental portions ofwater are added to form an emulsion of the aminofunctionalorganopolysiloxane.

Mixing in step (II) can be accomplished by any method known in the artto effect mixing of high viscosity materials. The mixing may occureither as a batch, semi-continuous, or continuous process. Any of themixing methods as described for step (I), may be used to effect mixingin step (II). Alternatively, mixing in step (II) may also occur viathose techniques known in the art to provide high shear mixing to effectformation of emulsions. Representative of such high shear mixingtechniques include; homongenizers, sonolators, and other similar sheardevices.

Optionally, the emulsion formed in step (II) may be further sheared ordiluted according to step (III) to reduce particle size and/or improvelong term storage stability and/or improve handling. The shearing mayoccur by any of the mixing techniques discussed above. In some cases itmight be necessary to run one or several of the steps I to III underlower pressure or vacuum.

The emulsion products of the present disclosure may be an oil/wateremulsion, a water/oil emulsion, a multiple phase or triple emulsion.

In one embodiment, the emulsion products of the present disclosure areoil/water emulsions. The present oil/water emulsions may becharacterized by average volume particle of the dispersed organosiloxaneblock copolymer (oil) phase in the continuous aqueous phase. Theparticle size may be determined by laser diffraction of the emulsion.Suitable laser diffraction techniques are well known in the art. Theparticle size is obtained from a particle size distribution (PSD). ThePSD can be determined on a volume, surface, length basis. The volumeparticle size is equal to the diameter of the sphere that has the samevolume as a given particle. The term Dv represents the average volumeparticle size of the dispersed particles. Dv 0.5 is the particle sizemeasured in volume corresponding to 50% of the cumulative particlepopulation. In other words if Dv 0.5=10 μm, 50% of the particle have anaverage volume particle size below 10 μm and 50% of the particle have avolume average particle size above 10 μm. Unless indicated otherwise allaverage volume particle sizes are calculated using Dv 0.5.

The average volume particle size of the dispersed siloxane particles inthe oil/water emulsions may vary between 0.1 μm and 150 μm; or between0.1 μm and 30 μm; or between 0.2 μm and 5.0 μm.

In one embodiment, the present aminofunctional silicone emulsions may becharacterized as having less than 0.1 weight % of D4 and D5 cyclicsiloxanes. Furthermore, the present aminofunctional silicone emulsionsmay be characterized as maintaining a low level upon aging of theemulsion. The aging of the present emulsions may be evaluated by storingthe emulsion for one month at 50° C. and measuring the D4 and D5 contentby gas chromatography (GC) techniques. Upon aging for one month at 50°C. the content D4, D5 or both in the present emulsion is lower than oneof the following:

0.1 wt. % for D4 or 0.1 wt. % for D5 for the emulsion,

-   -   below 0.14 for D4 or 0.07 for D5, when the content is expressed        as ratio of the cyclic to the non-water content of the cationic        surfactant,

below 1.3 for D4 when the content of the later is expressed as

-   -   ((D⁴ _(AGED)−D⁴ _((t=0)))/% CS)*100, where D4 is wt % the        percentage of D4 in the aged and starting emulsion respectively        and % CS is the mass fraction of the cationic surfactant        (non-water content) in the emulsion.

The present emulsions are useful to treat a variety of fiber surfaces.The fiber surfaces include various textile and natural fibers. Fibers ortextiles that can be treated with the treatment composition includenatural fibers such as cotton, silk, linen, and wool; regenerated fiberssuch as rayon and acetate; synthetic fibers such as polyesters,polyamides, polyacrylonitriles, polyethylenes, and polypropylenes;combinations, and blends thereof. The form of the fibers can includethreads, filaments, tows, yarns, woven fabrics, knitted materials,non-woven materials, paper, carpet, and leather.

The fiber treatment composition comprising the present emulsions can beapplied to the fiber and/or textile during making the fibers ortextiles, or later via a post application process. After application,carriers (if any) can be removed from the treatment composition forexample by drying the composition at ambient or elevated temperature.The amount of treatment composition applied to the fibers and textilesis typically sufficient to provide 0.1 to 15 weight percent of thecomposition on the fibers and textiles, based on their dry weight,preferably in an amount of 0.2 to 5 weight percent based on the dryweight of the fiber or textile.

The use of the compositions according to the invention on hair may use aconventional manner for conditioning hair. An effective amount of thecomposition for conditioning hair is applied to the hair. Such effectiveamounts generally range from about 0.5 g to about 50 g, preferably fromabout 1 g to about 20 g. Application to the hair typically includesworking the composition through the hair such that most or all of thehair is contacted with the composition. This method for conditioning thehair comprises the steps of applying an effective amount of the haircare composition to the hair, and then working the composition throughthe hair.

The present aminofunctional silicone compositions, or emulsions thereof,may be formulated into personal care product compositions. The personalcare compositions of this invention may be in the form of a cream, agel, a powder, a paste, or a freely pourable liquid. Generally, suchcompositions can generally be prepared at room temperature if no solidmaterials at room temperature are presents in the compositions, usingsimple propeller mixers, Brookfield counter-rotating mixers, orhomogenizing mixers. No special equipment or processing conditions aretypically required. Depending on the type of form made, the method ofpreparation will be different, but such methods are well known in theart.

The personal care products may be functional with respect to the portionof the body to which they are applied, cosmetic, therapeutic, or somecombination thereof. Conventional examples of such products include, butare not limited to: antiperspirants and deodorants, skin care creams,skin care lotions, moisturizers, facial treatments such as acne orwrinkle removers, personal and facial cleansers, bath oils, perfumes,colognes, sachets, sunscreens, pre-shave and after-shave lotions,shaving soaps, and shaving lathers, hair shampoos, hair conditioners,hair colorants, hair relaxants, hair sprays, mousses, gels, permanents,depilatories, and cuticle coats, make-ups, color cosmetics, foundations,concealers, blushes, lipsticks, eyeliners, mascara, oil removers, colorcosmetic removers, and powders, medicament creams, pastes or spraysincluding antiacne, dental hygienic, antibiotic, healing promotive,nutritive and the like, which may be preventative and/or therapeutic. Ingeneral the personal care products may be formulated with a carrier thatpermits application in any conventional form, including but not limitedto liquids, rinses, lotions, creams, pastes, gels, foams, mousses,ointments, sprays, aerosols, soaps, sticks, soft solids, solid gels, andgels. What constitutes a suitable carrier is readily apparent to one ofordinary skill in the art.

In yet another aspect the present emulsions can be used as part ofcolorant of fixative compositions and applied as pre-, during-,post-treatment in the process of coloring or perming hair. The purposescould range from color retention and color enhancement to againconditioning of the colored hair fibers. Examples and preferredembodiments can be found in the patent documents EP1312343A2,EP1312348A2, EP1312349A2, EP1312337, EP1312650, EP1312342 A2, EP1312341A2, WO2007071684, US20080282482 by L'Oreal and EP1543820 by Procter andGamble, all of which are incorporated herein by reference.

The compositions according to this invention can be used by the standardmethods, such as applying them to the human body, e.g. skin or hair,using applicators, brushes, applying by hand, pouring them and/orpossibly rubbing or massaging the composition onto or into the body.Removal methods, for example for color cosmetics are also well knownstandard methods, including washing, wiping, peeling and the like. Foruse on the skin, the compositions according to the present invention maybe used in a conventional manner for example for conditioning the skin.An effective amount of the composition for the purpose is applied to theskin. Such effective amounts generally range from about 1 mg/cm2 toabout 3 mg/cm2. Application to the skin typically includes working thecomposition into the skin. This method for applying to the skincomprises the steps of contacting the skin with the composition in aneffective amount and then rubbing the composition into the skin. Thesesteps can be repeated as many times as desired to achieve the desiredbenefit.

The use of the compositions according to the invention on hair may use aconventional manner for conditioning hair. An effective amount of thecomposition for conditioning hair is applied to the hair. Such effectiveamounts generally range from about 0.5 g to about 50 g, preferably fromabout 1 g to about 20 g. Application to the hair typically includesworking the composition through the hair such that most or all of thehair is contacted with the composition. This method for conditioning thehair comprises the steps of applying an effective amount of the haircare composition to the hair, and then working the composition throughthe hair. These steps can be repeated as many times as desired toachieve the desired conditioning benefit.

Non-limiting examples of additives which may be formulated into thepersonal care compositions in addition to the present aminofunctionalsilicone compositions include: additional silicones, anti-oxidants,cleansing agents, colorants, additional conditioning agents, depositionagents, electrolytes, emollients and oils, exfoliating agents, foamboosters, fragrances, humectants, occlusive agents, pediculicides, pHcontrol agents, pigments, preservatives, biocides, other solvents,stabilizers, sun-screening agents, suspending agents, tanning agents,other surfactants, thickeners, vitamins, botanicals, fragrances, waxes,rheology-modifying agents, anti-dandruff, anti-acne, anti-carrier andwound healing-promotion agents.

The personal care composition, such as a shampoo or cleanser may containat least one anionic detersive surfactant. This can be any of thewell-known anionic detersive surfactants typically used in shampooformulations. These anionic detersive surfactants function as cleansingagents and foaming agents in the shampoo compositions of this invention.The anionic detersive surfactants are exemplified by alkali metalsulfonates, sulfonated glyceryl esters of fatty acids such as sulfonatedmonoglycerides of coconut oil acids, salts of sulfonated monovalentalcohol esters such as sodium oleylisethianate, amides of amino sulfonicacids such as the sodium salt of oleyl methyl tauride, sulfonatedproducts of fatty acids nitriles such as palmitonitrile sulfonate,sulfonated aromatic hydrocarbons such as sodium alpha-naphthalenemonosulfonate, condensation products of naphthalene sulfonic acids withformaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkylsulfates such as sodium lauryl sulfate, ammonium lauryl sulfate ortriethanol amine lauryl sulfate, ether sulfates having alkyl groups of 8or more carbon atoms such as sodium lauryl ether sulfate, ammoniumlauryl ether sulfate, sodium alkyl aryl ether sulfates, and ammoniumalkyl aryl ether sulfates, alkylarylsulfonates having 1 or more alkylgroups of 8 or more carbon atoms, alkylbenzenesulfonic acid alkali metalsalts exemplified by hexylbenzenesulfonic acid sodium salt,octylbenzenesulfonic acid sodium salt, decylbenzenesulfonic acid sodiumsalt, dodecylbenzenesulfonic acid sodium salt, cetylbenzenesulfonic acidsodium salt, and myristylbenzenesulfonic acid sodium salt, sulfuricesters of polyoxyethylene alkyl ether includingCH3(CH2)6CH2O(C2H4O)2SO3H, CH3(CH2)7CH2O(C2H4O)3.5SO3H,CH3(CH2)8CH2O(C2H4O)8SO3H, CH3(CH2)19CH2O(C2H4O)4SO3H, andCH3(CH2)10CH2O(C2H4O)6SO3H, sodium salts, potassium salts, and aminesalts of alkylnaphthylsulfonic acid. Preferably the detersive surfactantis selected from the group consisting of sodium lauryl sulfate, ammoniumlauryl sulfate, triethanolamine lauryl sulfate, sodium lauryl ethersulfate, and ammonium lauryl ether sulfate. The anionic detersivesurfactant is present in the shampoo compositions of this invention inan amount from about 5 to 50 wt % and preferably about 5 to 25 wt %based on the total weight of the composition.

The personal care composition may contain at least one cationicdeposition aid, preferably a cationic deposition polymer. The cationicdeposition aid will generally be present at levels of from 0.001 to 5%,preferably from about 0.01 to 1%, more preferably from about 0.02% toabout 0.5% by weight. The polymer may be a homopolymer or be formed fromtwo or more types of monomers. The molecular weight of the polymer willgenerally be between 5 000 and 10 000 000, typically at least 10 000 andpreferably in the range 100 000 to about 2 000 000. The polymers willhave cationic nitrogen containing groups such as quaternary ammonium orprotonated amino groups, or a mixture thereof. The cationic chargedensity has been found to need to be at least 0.1 meq/g, preferablyabove 0.8 or higher. The cationic charge density should not exceed 4meq/g, it is preferably less than 3 and more preferably less than 2meq/g. The charge density can be measured using the Kjeldahl method andshould be within the above limits at the desired pH of use, which willin general be from about 3 to 9 and preferably between 4 and 8. Thecationic nitrogen-containing group will generally be present as asubstituent on a fraction of the total monomer units of the cationicdeposition polymer. Thus when the polymer is not a homopolymer it cancontain spacer noncationic monomer units. Such polymers are described inthe CTFA Cosmetic Ingredient Directory, 3rd edition. Suitable cationicdeposition aids include, for example, copolymers of vinyl monomershaving cationic amine or quaternary ammonium functionalities with watersoluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl(meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinylpyrrolidine. The alkyl and dialkyl substituted monomers preferably haveCI-C7 alkyl groups, more preferably C1-3 alkyl groups. Other suitablespacers include vinyl esters, vinyl alcohol, maleic anhydride, propyleneglycol and ethylene glycol. The cationic amines can be primary,secondary or tertiary amines, depending upon the particular species andthe pH of the composition. In general secondary and tertiary amines,especially tertiary, are preferred. Amine substituted vinyl monomers andamines can be polymerized in the amine form and then converted toammonium by quaternization. Suitable cationic amino and quaternaryammonium monomers include, for example, vinyl compounds substituted withdialkyl aminoalkyl acrylate, dialkylamino alkylmethacrylate,monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkylmethacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt,diallyl quaternary ammonium salts, and vinyl quaternary ammoniummonomers having cyclic cationic nitrogen-containing rings such aspyridinium, imidazolium, and quaternized pyrrolidine, e.g., alkyl vinylimidazolium, and quaternized pyrrolidine, e.g., alkyl vinyl imidazolium,alkyl vinyl pyridinium, alkyl vinyl pyrrolidine salts. The alkylportions of these monomers are preferably lower alkyls such as theC,-C., alkyls, more preferably C, and C2 alkyls. Suitableamine-substituted vinyl monomers for use herein includedialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate,dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide. Thecationic deposition aids can comprise mixtures of monomer units derivedfrom amine- and/or quaternary ammonium-substituted monomer and/orcompatible spacer monomers. Suitable cationic deposition aids include,for example: copolymers of 1-vinyl-2-pyrrolidine and1-vinyl-3-methylimidazolium salt (e.g., Chloride salt) (referred to inthe industry by the Cosmetic, Toiletry, and Fragrance Association,“CTFA”. as Polyquaternium-16) such as those commercially available fromBASF Wyandotte Corp. (Parsippany, N.J., USA) under the LUVIQUATtradename (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidineand dimethylaminoethyl methacrylate (referred to in the industry by CTFAas Polyquaternium-11) such as those commercially from Gar Corporation(Wayne, N.J., USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N);cationic diallyl quaternary ammonium-containing polymer including, forexample, dimethyldiallyammonium chloride homopolymer and copolymers ofacrylamide and dimethyldiallyammonium chloride, referred to in theindustry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;mineral acid salts of aminoalkyl esters of homo- and co-polymers ofunsaturated carboxylic acids having from 3 to 5 carbon atoms, asdescribed in U.S. Pat. No. 4,009,256; and cationic polyacrylamides asdescribed in our copending UK Application No. 9403156.4 (WO95/22311).Other cationic deposition aids that can be used include polysaccharidepolymers, such as cationic cellulose derivatives and cationic starchderivatives. Cationic polysaccharide polymer materials suitable for usein compositions of the invention include those of the formula:A-O(R—N⁺R¹R²R³X⁻) wherein: A is an anhydroglucose residual group, suchas starch or cellulose anhydroglucose residual, R is an alkyleneoxyalklene, polyoxyalkylene, or hydroxyalkylene group, or combinationthereof, R′, R˜′ and R3 independently are alkyl, aryl, alkylaryl,arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing upto about 18 carbon atoms, and the total number of carbon atoms for eachcationic moiety (i.e., the sum of carbon atoms in R′, R 2 and R′)preferably being about 20 or less, and X is an anionic counterion, aspreviously described. Cationic cellulose is available from AmercholCorp. (Edison, N.J., USA) in their Polymer iR (trade mark) and LR (trademark) series of polymers, as salts of hydroxyethyl cellulose reactedwith trimethyl ammonium substituted epoxide, referred to in the industry(CTFA) as Polyquaternium 10. Another type of cationic cellulose includesthe polymeric quaternary ammonium salts of hydroxyethyl cellulosereacted with lauryl dimethyl ammonium-substituted epoxide, referred toin the industry (CTFA) as Polyquaternium 24. These materials areavailable from Amerchol Corp. (Edison, N.J., USA) under the tradenamePolymer LM-200. Other cationic deposition aids that can be used includecationic guar gum derivatives, such as guar hydroxypropyltrimoniumchloride (Commercially available from Celanese Corp. in their Jaguartrademark series). Other materials include quaternarynitrogen-containing cellulose ethers (e.g., as described in U.S. Pat.No. 3,962,418, incorporated by reference herein), and copolymers ofetherified cellulose and starch (e.g., as described in U.S. Pat. No.3,958,581, incorporated by reference herein).

The personal care composition may contain a foam boosting agent. A foambooster is an agent which increases the amount of foam available from asystem at a constant molar concentration of surfactant, in contrast to afoam stabilizer which delays the collapse of a foam. Foam building isprovided by adding to the aqueous media an effective amount of a foamboosting agent. The foam boosting agent is preferably selected from thegroup consisting of fatty acid alkanolamides and amine oxides. The fattyacid alkanolamides are exemplified by isostearic acid diethanolamide,lauric acid diethanolamide, capric acid diethanolamide, coconut fattyacid diethanolamide, linoleic acid diethanolamide, myristic aciddiethanolamide, oleic acid diethanolamide, stearic acid diethanolamide,coconut fatty acid monoethanolamide, oleic acid monoisopropanolamide,and lauric acid monoisopropanolamide. The amine oxides are exemplifiedby N-cocodimethylamine oxide, N-lauryl dimethylamine oxide, N-myristyldimethylamine oxide, N-stearyl dimethylamine oxide, N-cocamidopropyldimethylamine oxide, N-tallowamidopropyl dimethylamine oxide,bis(2-hydroxyethyl) C12-15 alkoxypropylamine oxide. Preferably a foambooster is selected from the group consisting of lauric aciddiethanolamide, N-lauryl dimethylamine oxide, coconut aciddiethanolamide, myristic acid diethanolamide, and oleic aciddiethanolamide. The foam boosting agent is preferably present in theshampoo compositions of this invention in an amount from about 1 to 15wt % and more preferably about 2 to 10 wt % based on the total weight ofthe composition. The composition may further comprise a polyalkyleneglycol to improve lather performance. Concentration of the polyalkyleneglycol in the shampoo composition may range from about 0.01% to about5%, preferably from about 0.05% to about 3%, and more preferably fromabout 0.1% to about 2%, by weight of the composition. The optionalpolyalkylene glycols are characterized by the general formula:H(OCH2CHR)n-OH wherein R is selected from the group consisting of H,methyl, and mixtures thereof. When R is H, these materials are polymersof ethylene oxide, which are also known as polyethylene oxides,polyoxyethylenes, and polyethylene glycols. When R is methyl, thesematerials are polymers of propylene oxide, which are also known aspolypropylene oxides, polyoxypropylenes, and polypropylene glycols. WhenR is methyl, it is also understood that various positional isomers ofthe resulting polymers can exist. In the above structure, n has anaverage value of from about 1500 to about 25,000, preferably from about2500 to about 20,000, and more preferably from about 3500 to about15,000. Polyethylene glycol polymers useful herein are PEG-2M wherein Requals H and n has an average value of about 2,000 (PEG-2M is also knownas Polyox WSR9 N-10, which is available from Union Carbide and asPEG-2,000); PEG-5M wherein R equals H and n has an average value ofabout 5,000 (PEG-5M is also known as Polyox WSRO N-35 and Polyox WSRSN-80, both available from Union Carbide and as PEG-5,000 andPolyethylene Glycol 300,000); PEG-7M wherein R equals H and n has anaverage value of about 7,000 (PEG-7M is also known as Polyox WSRO N-750available from Union Carbide); PEG-9M wherein R equals H and n has anaverage value of about 9,000 (PEG 9-M is also known as Polyox WSRSN-3333 available from Union Carbide); and PEG14 M wherein R equals H andn has an average value of about 14,000 (PEG-14M is also known as PolyoxWSRO N-3000 available from Union Carbide). Other useful polymers includethe polypropylene glycols and mixed polyethylene/polypropylene glycols.

The personal care composition may contain a suspending agent atconcentrations effective for suspending the preferred siliconeconditioning agent, or other water-insoluble material, in dispersed formin the shampoo compositions. Such concentrations range from about 0.1%to about 10%, preferably from about 0.3% to about 5.0%, by weight of theshampoo compositions. Suspending agents include crystalline suspendingagents which can be categorized as acyl derivatives, long chain amineoxides, and mixtures thereof, concentrations of which range from about0.1% to about 5.0%, preferably from about 0.5% to about 3.0%, by weightof the shampoo compositions. These suspending agents are described inU.S. Pat. No. 4,741,855, which description is incorporated herein byreference. These preferred suspending agents include ethylene glycolesters of fatty acids preferably having from about 16 to about 22 carbonatoms. More preferred are the ethylene glycol stearates, both mono anddistearate, but particularly the distearate containing less than about7% of the mono stearate. Other suitable suspending agents includealkanol amides of fatty acids, preferably having from about 16 to about22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferredexamples of which include stearic monoethanolamide, stearicdiethanolamide, stearic monoisopropanolamide and stearicmonoethanolamide stearate. Other long chain acyl derivatives includelong chain esters of long chain fatty acids (e.g., stearyl stearate,cetyl palmitate, etc.); glyceryl esters (e.g., glyceryl distearate) andlong chain esters of long chain alkanol amides (e.g., stearamidediethanolamide distearate, stearamide monoethanolamide stearate). Longchain acyl derivatives, ethylene glycol esters of long chain carboxylicacids, long chain amine oxides, and alkanol amides of long chaincarboxylic acids in addition to the preferred materials listed above maybe used as suspending agents. For example, it is contemplated thatsuspending agents with long chain hydrocarbyls having C8-C22 chains maybe used. Other long chain acyl derivatives suitable for use assuspending agents include N,N-dihydrocarbyl amido benzoic acid andsoluble salts thereof (e.g., Na, K), particularly N,N-di(hydrogenated)C16, C18 and tallow amido benzoic acid species of this family, which arecommercially available from Stepan Company (Northfield, Ill., USA).Examples of suitable long chain amine oxides for use as suspendingagents include alkyl (C16-C22) dimethyl amine oxides, e.g., stearyldimethyl amine oxide. Other suitable suspending agents include xanthangum at concentrations ranging from about 0.3% to about 3%, preferablyfrom about 0.4% to about 1.2%, by weight of the shampoo compositions.The use of xanthan gum as a suspending agent in silicone containingshampoo compositions is described, for example, in U.S. Pat. No.4,788,006, which description is incorporated herein by reference.Combinations of long chain acyl derivatives and xanthan gum may also beused as a suspending agent in the shampoo compositions. Suchcombinations are described in U.S. Pat. No. 4,704,272, which descriptionis incorporated herein by reference. Other suitable suspending agentsinclude carboxyvinyl polymers. Preferred among these polymers are thecopolymers of acrylic acid crosslinked with polyallylsucrose asdescribed in U.S. Pat. No. 2,798,053, which description is incorporatedherein by reference. Examples of these polymers include Carbopol 934,940, 941, and 956, available from B. F. Goodrich Company. Other suitablesuspending agents include primary amines having a fatty alkyl moietyhaving at least about 16 carbon atoms, examples of which includepalmitamine or stearamine, and secondary amines having two fatty alkylmoieties each having at least about 12 carbon atoms, examples of whichinclude dipalmitoylamine or di(hydrogenated tallow)amine. Still othersuitable suspending agents include di(hydrogenated tallow)phthalic acidamide, and crosslinked maleic anhydride-methyl vinyl ether copolymer.Other suitable suspending agents may be used in the shampoocompositions, including those that can impart a gel-like viscosity tothe composition, such as water soluble or colloidally water solublepolymers like cellulose ethers (e.g., methylcellulose, hydroxybutylmethylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose,hydroxyethyl ethylcellulose and hydroxyethylcellulose), guar gum,polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starchand starch derivatives, and other thickeners, viscosity modifiers,gelling agents, etc.

EXAMPLES

The following examples are included to demonstrate the invention tothose of skill in the art. However, those of skill in the art should, inlight of the present disclosure, appreciate that many changes can bemade in the specific embodiments which are disclosed and still obtain alike or similar result without departing from the spirit and scope ofthe invention. All percentages are in wt. %. All measurements wereconducted at 23° C. unless indicated otherwise.

Comparative Aminofunctional Organopolysiloxanes

The following are commercially available aminofunctionalorganopolysiloxanes used as comparative examples. Their physicalcharacteristics listed are taken from the corresponding MSDS and/ortechnical documentation sheets.

AP-8087

A 5000 cP, Dimethyl, Methyl Aminoethylaminoisobutyl siloxane, methoxy &hydroxyl terminated, commercially available under the name DowCorning®AP-8087 (Dow Corning Corp., Midland, Mich.)

AP-8566 A

3500 cSt Dimethyl, methyl (aminoethylaminoisobutyl) siloxane, nitrogencontent of less 1%, 1-5% cyclic siloxanes, commercially available underthe name DowCorning® AP-8566. (Dow Corning Corp., Midland, Mich.)

AP-8468

A 5000-15000 cP Dimethyl, (aminoethylaminopropyl) methyl siloxane withnitrogen content of 0.6%, Available as OFX-8468 FLUID from Xiameter (DowCorning Corp., Midland, Mich.).

Example 1

Preparation of Amino Functional Silicone Composition AP1

First, 490 g of a OH-terminated polydimethylsiloxane (DOW CORNING®2-1273 FLUID), 3.75 g of hexamethyldisilazane, and 0.1 g oftrifluoroacetic acid were added to a 1 L 3-necked round-bottomed flaskfitted with a crescent-shaped paddle stirring rod, a water cooledcondenser and a thermometer adaptor itself fitted with a thermal couple,all under nitrogen purge. The reaction mixture was heated to 70° C. atmoderate stirring and held for 3 h reflux and then 6.67 g ofaminoethylaminopropylmethyldimethoxysilane was added to the reactionfollowed by the addition of a small amount 0.2 wt. % Octanoic acid. Thereaction continued at 80° C. and reflux for 3 h. 24 h later the reactionmixture was stripped for 10 h at 94° C. and under reduced pressure andmoderate stirring. The resulting aminofunctional organosiloxane appearedclear and colorless. 29Si NMR was used to characterize the polymer and aDP of 319 is obtained from the ratio between D and M units. Theviscosity was 2024 cP as measured by means of a Brookfield RV DVviscometer equipped with Pro CP 52 spindle at 20 RPM at 25 C. The % Nwas obtained by titration and was 0.16%. Molecular weight was obtainedusing standard GPC with polystyrene standards, the amount of cyclicsilicones was determined by means of Gas Chromatography. Values areprovided in Table 1.

Example 2

Preparation of an Amino Functional Silicone Composition AP2

Essentially the same process was used as in Example 1. First 477 g ofthe OH-terminated polydimethylsiloxane and 9.9 g ofethoxytrimethylsilane instead of hexamethyldisilazane were used. Thisprocess results in a clear colorless polymer with DP of 269 (valueobtained by NMR); viscosity of 1769 cP and % N of 0.16%. Furthercharacteristics are provided in Table 1.

TABLE 1 FRESH Ex 1 Ex 2 Mn g/mol 21,200 22,800 Mw g/mol 42,700 42,100 Mzg/mol 77,700 70,500 ppm D4. <5 <5 ppm D5. <5 <5 viscosity, cP 2024 1761

Example 3

Different amino polymers were formulated in a shampoo and the influenceof the polymer on the viscosity of the formulation was observed. Anamino polymer of preparation Example 2 and AP-8087 do not decrease theinitial viscosity of the formulation. The incorporation of the AP 8566or AP-8468 decreases the viscosity by a factor of 3 to 4 (Table 2).Moreover, over their usable shelf life, the formulations containing AP2and AP-8087 have a substantially higher viscosity than the formulationscontaining AP-8566 or AP-8468 (compare samples A1-Ref to A2-A5 at thesame storage time in table 2). However, AP-8087 is methoxy-terminatedorganopolysiloxane and tends to self-condense upon storage, which is adisadvantage in industrial setting.

TABLE 2 Ingredients A1-REF A2 A3 A4 A5 Phase Empicol ESB3 30.0% 30.0%30.0% 30.0% 30.0% A Water to 100% to 100% to 100% to 100% to 100%Glucamate  1.5%  1.5%  1.5%  1.5%  1.5% DOE120 Rewoderm  4.0%  4.0% 4.0%  4.0%  4.0% S1333 Amonyl 380BA  4.0%  4.0%  4.0%  4.0%  4.0% PhaseComperlan KD  4.0%  4.0%  4.0%  4.0%  4.0% B Phase Polymer of   2% CInvention AP2 active AP-8087   2% active AP-8566   2% active AP-8468  2% active Phase Citric q.s. q.s. q.s. q.s. q.s. D acid (50%) to pH =5.5 Appearance Clear Slightly Slightly Clear Clear white/ white/ greygrey opaque opaque viscosity, Just after 151000 123000 133000 3440042000 spindle 5, formulation 1 rpm 24 h 137000 98000 110000 32000 302001 week 193000 90400 104000 40400 35800 2 weeks 183000 82400 96400 3980036600 3 weeks 187000 81200 98400 38900 36800 1 month 191000 72800 9480039800 35800 3 months 168000 62000 84000 34100 30200 4 months 15400059600 78800 32200 28200 5 months 152000 52400 74000 29900 26200 6 months178000 56800 79600 32000 28500

Example 4

Polymers AP 8087, AP2 and AP-8468 were formulated in a rinse offformulation. Caucasian bleached hair tresses were treated with therinse-off conditioner formulations and forces required to drive a combthrough a tress of hair were measured using a Dia-Stron MTT-175(Dia-Stron Limited, UK). The test was run in an environmentallycontrolled room with a constant temperature of 20° C. and fixed relativehumidity of 50%. Total combing load was obtained from UvWin software.Statistical analysis was run with the data generated.

Generally the lower the combing force/load the better the performance.Without being bound to any theory, for the consumer the low combing loadtranslates into one or more of the following:

Ease of detangling

Less detangled

Ease of styling

Smooth/soft

Supple

Reduced friction

Easy to manage

The list above is not exhaustive and is meant solely to illustrate theimportance of the measurement value for the practice. A person skill inthe art will understand that different adjectives along the lines abovecan be used to describe hair characterized with a low dry or wet combingload. Hair tresses were treated with the rinse-off formulation and thecombing load was measured in wet and dry state. It has been found (table3) that rinse off comprising the polymer of the invention (AP2) provideslower combing load than the comparative examples. Values marked with *are statistically different from the polymer of the invention withp<0.01. (Table 3)

TABLE 3 Combing Load, J dry avg wet avg dry std dev wet std dev AP-84680.094* 0.881* 0.012 0.215 AP2 - invention 0.054 0.287 0.011 0.074AP-8087 0.066* 0.811* 0.011 0.171

Example 5

Emulsification

The polymer AP2 of the present invention was emulsified using shearequipment with capacity of 10 L. The AP2, surfactants (cationic andnonionic) and some water were put in the kettle and subjected tovigorous shear to produce emulsion via catastrophic phase inversion.Thus produced concentrated emulsion was then diluted to about 50%silicone. Then the thickener was dispersed followed by the adjustment ofthe pH to 7.2 by adding small amount of sulfuric acid. Last, acosmetically acceptable biocide has been added. Table 4 summarizes thecomposition of EM-AP2 emulsion.

TABLE 4 Ingredients in EM -AP2 % AP2 49.95 Arquad 16-29 (cationicsurfactant) 6.41 C13E6 (nonionic surfactant) 4.24 Cellulose basedthickener 0.25 Biocide 0.9 Water q.s. 100Shine/Luster Evaluation

EM-AP2 was formulated in hair care rinse-off conditioner. A comparativeexample is prepared using Dow Corning® 949 cationic emulsion. Caucasianbleached hair tresses were treated with the rinse-off conditionerformulations. Treatment level corresponds to 0.4 g formulatedrinse-off/1 g hair. The rinse-off formulations contained 2% Silicone.The tresses (treated and untreated; 3 independent tresses performulation, 3 reading points per tress) were evaluated for shine/lusterusing commercial Samba equipment from Bossa Nova Technologies. Theinstrument measures specular reflection (shine) and second reflection(chroma) and the diffuse reflection of light from the hair to determinethe luster value.

For the consumer the increase in luster value can also be expressed as:

Brilliance

Liveliness/Vitality

Healthy

The list above is not exhaustive and is meant solely to illustrate theimportance of the measurement value for the practice. A person skill inthe art will understand that different adjectives along the lines abovecan be used to describe hair characterized with increased shine/luster.

Upon treatment, the emulsion according to this invention provides forhigher shine than the commercial reference e.g. Dow Corning® 949cationic emulsion (Table 5)

TABLE 5 % change in luster Emulsion Code treated vs. untreated tresses ±STDEV EM-AP2 −4.4* ± 1.9 DC 949 −11.4 ± 4.9 *Statistically differentfrom the reference with confidentiality of 95%

The invention claimed is:
 1. A method of treating a surface of a fiber,the method comprising applying an aqueous emulsion to the surface of thefiber, wherein the aqueous emulsion comprises: A) an aminofunctionalsilicone composition comprising an organopolysiloxane having an averageformula:(CH₃)₃SiO[(CH₃)₂SiO]_(x)[(CH₃)R^(N)SiO]_(y)Si(CH₃)₃ with less than 1weight % of nitrogen in its formula, where R^(N) is an aminofunctionalgroup, x is ≥100, and y is ≥1, with the proviso that the sum of x+y isfrom 250 to 350; and B) a quaternary ammonium surfactant having aformula:R¹R²R³R⁴N⁺X⁻, where R¹ is a radical containing at least 10 carbon atoms,R² is R¹ or a hydrocarbyl containing 1 to 12 carbon atoms, R³ is R¹, R²,or an alcohol group containing 2 to 10 carbon atoms, R⁴ is R¹, R², orR³, and X⁻ is a halide, sulfate, sulfonate, methosulfate, orethosulfate; wherein the viscosity of A) the aminofunctional siliconecomposition ranges from 1000 to 2500 cP at 25° C. as measured by aBrookfield RV DV viscometer equipped with Pro CP 52 spindle at 20 RPM;wherein A) the aminofunctional silicone composition contains less than0.1 weight % of octamethylcyclotetrasiloxanes (D4) and less than 0.1weight % decamethylcyclopentasiloxanes (D5) cyclic siloxanes; andwherein B) the quaternary ammonium surfactant is present in the aqueousemulsion in an amount of at least 0.5 weight %.
 2. The method of claim1, wherein the aminofunctional group R^(N) has the formula—CH₂CH₂CH₂NHCH₂CH₂NH₂.
 3. The method of claim 1, wherein A) theaminofunctional silicone composition is present in the aqueous emulsionin an amount of from 15 to 80 weight %.
 4. The method of claim 1,wherein B) the quaternary ammonium surfactant is present in the aqueousemulsion in an amount of from 0.5 to 10 weight %.
 5. The method of claim1, wherein the aqueous emulsion further comprises: C) a nonionicsurfactant.
 6. The method of claim 5, wherein C) the nonionic surfactantis present in the aqueous emulsion in an amount of from 2 to 8 weight %.7. The method of claim 1, wherein: i) the fiber is selected from thegroup of natural fibers, regenerated fibers, synthetic fibers, andcombinations thereof; and/or ii) the fiber is selected from the group oftextiles, threads, filaments, tows, yarns, woven fabrics, knittedmaterials, non-woven materials, paper, carpet, leather, and combinationsthereof.
 8. The method of claim 1, further comprising the step of dryingthe surface of the fiber after application of the aqueous emulsion. 9.The method of claim 1, wherein the aqueous emulsion is applied in anamount to provide 0.1 to 15 weight % of the aqueous emulsion on thefiber based on dry weight of the fiber.